JP7056557B2 - Conductive polyamide resin composition - Google Patents

Conductive polyamide resin composition Download PDF

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JP7056557B2
JP7056557B2 JP2018510894A JP2018510894A JP7056557B2 JP 7056557 B2 JP7056557 B2 JP 7056557B2 JP 2018510894 A JP2018510894 A JP 2018510894A JP 2018510894 A JP2018510894 A JP 2018510894A JP 7056557 B2 JP7056557 B2 JP 7056557B2
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polyamide resin
resin composition
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carbon black
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JPWO2018147250A1 (en
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修司 久保田
信宏 吉村
雄平 福本
和樹 岩村
聖史 酒井
修 馬渕
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Description

本発明は、ポリアミド樹脂と導電性カーボンブラックおよびオレフィン系の樹脂を含有してなる導電性ポリアミド樹脂組成物に関するものである。さらに詳しくは、本発明は、導電性に優れるのみならず、耐燃料性、特にアルコール含有燃料に対して優れた耐燃料性を併せもち、燃料タンク用キャップなどに好適な導電性ポリアミド樹脂組成物に関するものである。 The present invention relates to a conductive polyamide resin composition containing a polyamide resin, conductive carbon black, and an olefin-based resin. More specifically, the present invention has not only excellent conductivity but also fuel resistance, particularly excellent fuel resistance to alcohol-containing fuels, and is a conductive polyamide resin composition suitable for a cap for a fuel tank or the like. It is about.

ポリアミド樹脂は、ガソリン等の有機溶剤やアルカリ液に対して優れた耐薬品性を示すと共に、流動性が高く、耐熱性、耐クリープ性に優れるため、自動車の外装材やエンジンルーム内部品として用いられている。また、さらにカーボンブラック等を配合して導電性を付与し、静電気の発生・帯電を抑制し、比較的短時間で放電可能な機能を持たせて、自動車部品の給油系統部品として用いられている。 Polyamide resin has excellent chemical resistance to organic solvents such as gasoline and alkaline liquids, and has high fluidity, heat resistance, and creep resistance, so it is used as an exterior material for automobiles and parts in engine rooms. Has been done. In addition, carbon black and the like are blended to impart conductivity, suppress the generation and charging of static electricity, and have the function of being able to discharge in a relatively short time, and are used as refueling system parts for automobile parts. ..

ポリアミド樹脂に導電性を付与するために、ポリアミド樹脂にカーボンブラックを配合することは良く知られているが、導電性を向上させるためにカーボンブラックの配合量を増やすと組成物の成形性、流動性、物性などにおいて様々な解決すべき欠点が認められ、それぞれ対策が提案されている。例えば、流動性や成形性を改良するため、ポリアミド樹脂にカーボンブラックと変性されたエチレン共重合体を配合することが提案され（特許文献１参照）、導電性と耐衝撃性を両立させる方法として、カーボンブラックの分散剤を配合する方法が提案され（特許文献２参照）、さらには、組成物のモルフォロジー構造を特定化することにより導電性、耐衝撃性および優れた摺動特性を発現させる提案（特許文献３参照）などがある。 It is well known to add carbon black to a polyamide resin in order to impart conductivity to the polyamide resin, but if the amount of carbon black to be added is increased in order to improve the conductivity, the composition can be molded and flowed. Various shortcomings to be solved have been recognized in terms of properties and physical properties, and countermeasures have been proposed for each. For example, in order to improve fluidity and moldability, it has been proposed to add carbon black and a modified ethylene copolymer to a polyamide resin (see Patent Document 1), as a method for achieving both conductivity and impact resistance. , A method of blending a dispersant of carbon black has been proposed (see Patent Document 2), and further, a proposal of exhibiting conductivity, impact resistance and excellent sliding properties by specifying the morphological structure of the composition. (See Patent Document 3) and the like.

特開昭５８－９３７５６号公報Japanese Unexamined Patent Publication No. 58-93756 特開平１１－１８０１７１号公報Japanese Unexamined Patent Publication No. 11-180171 特開２００６－２５７４２９号公報Japanese Unexamined Patent Publication No. 2006-257429

提案された方法によれば、それぞれに改善効果が認められるが、耐衝撃性に優れる樹脂組成物の場合、燃料に接触する環境下、特に、アルコール含有燃料に接触する環境下では、導電性が低下してくる欠点があることが判明した。 According to the proposed method, improvement effects are recognized for each, but in the case of a resin composition having excellent impact resistance, conductivity is obtained in an environment in contact with fuel, particularly in an environment in contact with alcohol-containing fuel. It turns out that there are drawbacks that are decreasing.

本発明は、上述の従来技術の現状に鑑み創案されたものであり、その目的は、ポリアミド樹脂にカーボンブラックを配合した導電性ポリアミド樹脂組成物において、導電性に優れるのみならず、耐燃料性、特にアルコール含有燃料に対して優れた耐燃料性を併せもち、さらには流動性が高く成形性に優れ、耐衝撃性に優れた成形品の成形が可能で、燃料タンク用キャップなどの成形品の提供を可能とする導電性ポリアミド樹脂組成物を提供することにある。 The present invention has been invented in view of the current state of the prior art described above, and an object thereof is to provide a conductive polyamide resin composition in which carbon black is blended with a polyamide resin, which not only has excellent conductivity but also has fuel resistance. In particular, it has excellent fuel resistance against alcohol-containing fuels, and it is possible to mold molded products with high fluidity, excellent moldability, and excellent impact resistance, and molded products such as fuel tank caps. It is an object of the present invention to provide a conductive polyamide resin composition which enables the provision of the above.

本発明者等は、上記課題を解決するために鋭意研究した結果、耐衝撃性付与や導電性カーボンブラックの分散のために配合したエチレン－αオレフィン共重合体が、アルコールを含有する燃料によって膨潤し、導電性カーボンブラックのカーボン粒子間の距離が、導電性消失が発生するほどまでに広がってしまうこと、及び導電性カーボンブラックの吸油性が主要な原因であることを突き止めた。そこで、導電性ポリエチレン樹脂を配合し、モルフォロジー構造を制御することで、上記課題を達成し得ることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have swelled the ethylene-α-olefin copolymer blended for imparting impact resistance and dispersing conductive carbon black by a fuel containing alcohol. However, it was found that the distance between the carbon particles of the conductive carbon black is widened to the extent that the loss of conductivity occurs, and that the oil absorption of the conductive carbon black is the main cause. Therefore, they have found that the above problems can be achieved by blending a conductive polyethylene resin and controlling the morphology structure, and have completed the present invention.

即ち、本発明は、以下の通りである。
［１］ ポリアミド樹脂（Ａ）８４～４０質量％、導電性カーボンブラック（Ｂ）５～３０質量％、ポリアミド樹脂の末端基および／又は主鎖のアミド基と反応しうる反応性官能基を有するエチレン－αオレフィン共重合体（Ｃ）３～３０質量％、および導電性ポリエチレン樹脂（Ｄ）１～２０質量％を含有してなり、下記の特性（イ）、（ロ）を満足することを特徴とする導電性ポリアミド樹脂組成物。
（イ）導電性ポリアミド樹脂組成物を射出成形することによって得た平板（１００ｍｍ×１００ｍｍ×２ｍｍ（厚み））の初期の体積固有抵抗が１×１０５Ω・ｃｍ以下で、該平板をＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗が１×１０７Ω・ｃｍ以下
（ロ）導電性ポリアミド樹脂組成物を射出成形することによって得た試験片の－４０℃におけるシャルピー衝撃強度が２．０ＫＪ／ｍ２以上
［２］ 前記導電性ポリアミド樹脂組成物が、下記の特性（ハ）を満足する［１］に記載の導電性ポリアミド樹脂組成物。
（ハ）温度２５０℃、荷重１０ｋｇｆで測定したメルトインデックスが、２ｇ／１０ｍｉｎ以上
［３］ 前記導電性ポリエチレン樹脂（Ｄ）のポリエチレンが、高密度ポリエチレンである［１］または［２］に記載の導電性ポリアミド樹脂組成物。That is, the present invention is as follows.
[1] Polyamide resin (A) has 84 to 40% by mass, conductive carbon black (B) has 5 to 30% by mass, and has a reactive functional group capable of reacting with the terminal group and / or the amide group of the main chain of the polyamide resin. It contains 3 to 30% by mass of the ethylene-α olefin copolymer (C) and 1 to 20% by mass of the conductive polyethylene resin (D), and satisfies the following characteristics (a) and (b). A characteristic conductive polyamide resin composition.
(A) The initial volume resistivity of the flat plate (100 mm × 100 mm × 2 mm (thickness)) obtained by injection molding the conductive polyamide resin composition is 1 × 10 5 Ω · cm or less, and the flat plate is used as a CM15 fuel. Volume resistivity after exposure to 168 hours is 1 × 10 7 Ω · cm or less (b) The sharpy impact strength of the test piece obtained by injection molding the conductive polyamide resin composition at -40 ° C is 2.0 KJ. / M 2 or more [2] The conductive polyamide resin composition according to [1], wherein the conductive polyamide resin composition satisfies the following property (c).
(C) The melt index measured at a temperature of 250 ° C. and a load of 10 kgf is 2 g / 10 min or more. [3] The polyethylene of the conductive polyethylene resin (D) is a high-density polyethylene, according to [1] or [2]. Conductive polyamide resin composition.

本発明の導電性ポリアミド樹脂組成物は、メタノールやエタノールなどのアルコールを含有する燃料に接触する環境下でも、導電性の低下が小さく、自動車の燃料系部品、例えば燃料タンクのキャップやストレーナー、フィルター、バルブ等の部品に使用することができる。 The conductive polyamide resin composition of the present invention has a small decrease in conductivity even in an environment in contact with a fuel containing alcohol such as methanol or ethanol, and has a small decrease in conductivity, and fuel system parts of automobiles such as fuel tank caps, strainers, and filters. , Can be used for parts such as valves.

以下に本発明を具体的に説明する。
本発明の導電性ポリアミド樹脂組成物は、ポリアミド樹脂（Ａ）８４～４０質量％、導電性カーボンブラック（Ｂ）５～３０質量％、ポリアミド樹脂の末端基および／又は主鎖のアミド基と反応しうる反応性官能基を有するエチレン－αオレフィン共重合体（Ｃ）３～３０質量％、および導電性ポリエチレン樹脂（Ｄ）１～２０質量％を含有してなり、下記の特性（イ）、（ロ）を満足することを特徴とする。
（イ）導電性ポリアミド樹脂組成物を射出成形することによって得た平板（１００ｍｍ×１００ｍｍ×２ｍｍ（厚み））の初期の体積固有抵抗が１×１０５Ω・ｃｍ以下で、該平板をＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗が１×１０７Ω・ｃｍ以下
（ロ）導電性ポリアミド樹脂組成物を射出成形することによって得た試験片の－４０℃におけるシャルピー衝撃強度が２．０ＫＪ／ｍ２以上The present invention will be specifically described below.
The conductive polyamide resin composition of the present invention reacts with 84 to 40% by mass of the polyamide resin (A), 5 to 30% by mass of the conductive carbon black (B), and the amide group of the terminal group and / or the main chain of the polyamide resin. It contains 3 to 30% by mass of an ethylene-α-olefin copolymer (C) having a possible reactive functional group and 1 to 20% by mass of a conductive polyethylene resin (D), and has the following characteristics (a). It is characterized by satisfying (b).
(A) The initial volume resistivity of the flat plate (100 mm × 100 mm × 2 mm (thickness)) obtained by injection molding the conductive polyamide resin composition is 1 × 10 5 Ω · cm or less, and the flat plate is used as CM15 fuel. Volume resistivity after exposure to 168 hours is 1 × 10 7 Ω · cm or less (b) The shearpy impact strength of the test piece obtained by injection molding the conductive polyamide resin composition at -40 ° C is 2.0 KJ. / M 2 or more

各成分の含有量は、導電性ポリアミド樹脂組成物中の割合（質量％）である。
特性（イ）は、後記する導電性ポリアミド樹脂組成物のモルフォロジー構造の制御により達成される。
ＣＭ１５燃料とは、Ｆｕｅｌ－Ｃ（イソオクタン／トルエン＝１／１（容量））にメタノールが１５質量％含まれたものである。The content of each component is a ratio (mass%) in the conductive polyamide resin composition.
The property (a) is achieved by controlling the morphological structure of the conductive polyamide resin composition described later.
The CM15 fuel is Fuel-C (isooctane / toluene = 1/1 (volume)) containing 15% by mass of methanol.

本発明の導電性ポリアミド樹脂組成物の導電性は、射出成形することによって得た平板（１００ｍｍ×１００ｍｍ×２ｍｍ（厚み））の初期の体積固有抵抗が１×１０５Ω・ｃｍ以下である。初期の体積固有抵抗は、５×１０４Ω・ｃｍ以下であることが好ましい。初期の体積固有抵抗の下限は、特に限定されないが、用いる原材料等から５×１０３Ω・ｃｍ程度である。The conductivity of the conductive polyamide resin composition of the present invention is such that the initial volume resistivity of the flat plate (100 mm × 100 mm × 2 mm (thickness)) obtained by injection molding is 1 × 10 5 Ω · cm or less. The initial volume resistivity is preferably 5 × 10 4 Ω · cm or less. The lower limit of the initial volume resistivity is not particularly limited, but is about 5 × 10 3 Ω · cm depending on the raw materials used.

本発明の導電性ポリアミド樹脂組成物の導電性は、燃料に接触する環境下、特に、アルコール含有燃料に接触する環境下であっても、導電性の低下を抑制でき、ＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗が１×１０７Ω・ｃｍ以下を達成できる。ＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗は、１×１０６Ω・ｃｍ以下が好ましく、５×１０５Ω・ｃｍ以下がより好ましい。暴露後の体積固有抵抗の下限は、特に限定されないが、用いる原材料等から５×１０４Ω・ｃｍ程度である。体積固有抵抗は、後記の実施例の項に記載の方法で測定できる。The conductivity of the conductive polyamide resin composition of the present invention can suppress a decrease in conductivity even in an environment in contact with fuel, particularly in an environment in contact with alcohol-containing fuel, and is exposed to CM15 fuel for 168 hours. The volume resistivity after this can be achieved to be 1 × 107 Ω · cm or less. The volume resistivity after exposure to the CM15 fuel for 168 hours is preferably 1 × 10 6 Ω · cm or less, and more preferably 5 × 10 5 Ω · cm or less. The lower limit of the volume resistivity after exposure is not particularly limited, but is about 5 × 10 4 Ω · cm depending on the raw materials used. The volume resistivity can be measured by the method described in the Examples section below.

また、低温耐衝撃性に優れ、－４０℃におけるシャルピー衝撃強度が２．０ＫＪ／ｍ２以上であり、導電性ポリアミド樹脂組成物が、後記する構成を取ることで達成できる。シャルピー衝撃強度は、好ましくは、２．５ＫＪ／ｍ２以上である。シャルピー衝撃強度の上限は、特に限定されないが、用いる原材料等から２０ＫＪ／ｍ２程度である。シャルピー衝撃強度は、後記の実施例の項に記載の方法で測定できる。Further, it is excellent in low temperature impact resistance, has a Charpy impact strength at −40 ° C. of 2.0 KJ / m 2 or more, and can be achieved by adopting a constitution described later in the conductive polyamide resin composition. The Charpy impact strength is preferably 2.5 KJ / m 2 or more. The upper limit of the Charpy impact strength is not particularly limited, but is about 20 KJ / m 2 depending on the raw materials used. The Charpy impact strength can be measured by the method described in the section of Examples described later.

さらに、本発明の導電性ポリアミド樹脂組成物は、流動性に優れることが好ましく、メルトインデックス（ＩＳＯ１１３３法、２５０℃、荷重１０ｋｇ）が２ｇ／１０分以上が好ましく、より好ましくは３ｇ／１０分以上、さらに好ましくは５ｇ／１０分以上、特に好ましくは１０ｇ／１０分以上である。メルトインデックスは、後記する各成分の量を調整することで、最適な範囲とすることができる。メルトインデックスの上限は、特に限定されないが、用いる原材料等から３０ｇ／１０分程度である。メルトインデックスは、後記の実施例の項に記載の方法で測定できる。 Further, the conductive polyamide resin composition of the present invention preferably has excellent fluidity, preferably has a melt index (ISO1133 method, 250 ° C., load 10 kg) of 2 g / 10 minutes or more, and more preferably 3 g / 10 minutes or more. It is more preferably 5 g / 10 minutes or more, and particularly preferably 10 g / 10 minutes or more. The melt index can be set to the optimum range by adjusting the amount of each component described later. The upper limit of the melt index is not particularly limited, but is about 30 g / 10 minutes from the raw materials used. The melt index can be measured by the method described in the Examples section below.

本発明で用いるポリアミド樹脂（Ａ）とは、分子中に酸アミド結合（－ＣＯＮＨ－）を有するものである。具体的には、ε－カプロラクタム、６－アミノカプロン酸、ω－エナントラクタム、７－アミノヘプタン酸、１１－アミノウンデカン酸、９－アミノノナン酸、α－ピロリドン、α－ピペリジンなどから得られる重合体または共重合体もしくはこれらのブレンド物、ヘキサメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、メタキシリレンジアミンなどのジアミンと、テレフタール酸、イソフタール酸、アジピン酸、セバシン酸などのジカルボン酸とを重縮合して得られる重合体または共重合体もしくはこれらのブレンド物等を例示することができるが、これらに限定されるものではない。入手のし易さから、ポリアミド６、ポリアミド６６が好ましい。 The polyamide resin (A) used in the present invention has an acid amide bond (-CONH-) in the molecule. Specifically, a polymer obtained from ε-caprolactam, 6-aminocaproic acid, ω-enantractum, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidine and the like or Copolymers or blends thereof, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine and other diamines, and terephthalic acid, isoftal acid, adipic acid, sebacic acid and other dicarboxylic acids. Examples of the polymer or copolymer obtained by polycondensing with, or a blend thereof, and the like can be exemplified, but the present invention is not limited thereto. Polyamide 6 and polyamide 66 are preferable because they are easily available.

これらのポリアミド樹脂の数平均分子量は７０００～３００００のものが好ましく用いられる。数平均分子量が７０００未満ではタフネスが低下する傾向があり、また３００００を越えると流動性が低下する傾向がある。相対粘度（９８％硫酸溶液中で測定）で表すと、１．５～４．０が好ましい。ポリアミド樹脂（Ａ）の含有量は、８４～４０質量％、より好ましくは７０～５０質量％である。ポリアミド樹脂が４０質量％未満になると、導電性ポリアミド樹脂組成物からなる成形品の微細構造において、ポリアミド樹脂が連続相となるべきモルフォロジー構造が不安定になり好ましくない。 The number average molecular weight of these polyamide resins is preferably 7,000 to 30,000. If the number average molecular weight is less than 7,000, the toughness tends to decrease, and if it exceeds 30,000, the fluidity tends to decrease. In terms of relative viscosity (measured in 98% sulfuric acid solution), 1.5 to 4.0 is preferable. The content of the polyamide resin (A) is 84 to 40% by mass, more preferably 70 to 50% by mass. When the amount of the polyamide resin is less than 40% by mass, the morphological structure in which the polyamide resin should be a continuous phase becomes unstable in the fine structure of the molded product made of the conductive polyamide resin composition, which is not preferable.

本発明で用いる導電性カーボンブラック（Ｂ）としては特に制限されるものではなく、ケッチェンブラック、アセチレンブラック、ファーネスブラックおよびチャンネルブラック等を使用することができる。これらの中ではケッチェンブラックが、少ない含有量で優れた導電性を発揮するため特に好ましい。導電性カーボンブラック（Ｂ）の含有量は、目的とする導電性の度合いにもよるが、５～３０質量％が好適である。導電性カーボンブラック（Ｂ）の含有量は、１５～３０質量％が好ましく、２０～３０質量％がより好ましい。 The conductive carbon black (B) used in the present invention is not particularly limited, and Ketjen black, acetylene black, furnace black, channel black and the like can be used. Among these, Ketjen Black is particularly preferable because it exhibits excellent conductivity with a small content. The content of the conductive carbon black (B) depends on the desired degree of conductivity, but is preferably 5 to 30% by mass. The content of the conductive carbon black (B) is preferably 15 to 30% by mass, more preferably 20 to 30% by mass.

これらの導電性カーボンブラックは、導電性ポリアミド樹脂組成物の連続相を形成するポリアミド樹脂中に、含有量の８０質量％以上分散することが好ましい。そのためには混練工程が極めて重要であると共に、カーボンブラックの粒子表面に存在するカルボキシル基や水酸基等の官能基も重要である。混錬工程で十分練ることによりカーボンブラックの表面の官能基が作用してポリアミド樹脂との親和性が増大し、ポリアミド樹脂の連続相に分散しやすくなる。本発明では、混錬条件やカーボンブラックの表面にある官能基濃度等は特に限定するものではなく、導電性ポリアミド樹脂組成物の成形品においてカーボンブラックの含有量の８０質量％以上が連続相であるポリアミド樹脂中に分散していることが重要である。このようなカーボンブラックの分散によって、体積固有抵抗が１×１０５Ω・ｃｍ以下の優れた導電性を持つ組成物が得られる。また他の物性値も良好となる。It is preferable that these conductive carbon blacks are dispersed in a polyamide resin forming a continuous phase of the conductive polyamide resin composition in an amount of 80% by mass or more of the content. For that purpose, the kneading step is extremely important, and functional groups such as carboxyl groups and hydroxyl groups present on the surface of carbon black particles are also important. By sufficiently kneading in the kneading step, the functional groups on the surface of carbon black act to increase the affinity with the polyamide resin, and it becomes easy to disperse in the continuous phase of the polyamide resin. In the present invention, the kneading conditions and the concentration of functional groups on the surface of the carbon black are not particularly limited, and 80% by mass or more of the carbon black content in the molded product of the conductive polyamide resin composition is a continuous phase. It is important that it is dispersed in a certain polyamide resin. By such dispersion of carbon black, a composition having excellent conductivity having a volume resistivity of 1 × 10 5 Ω · cm or less can be obtained. In addition, other physical property values are also good.

本発明で用いるポリアミド樹脂の末端基および／または主鎖のアミド基と反応しうる官能基を有するエチレン－αオレフィン共重合体（Ｃ）（以下、変性エチレン－αオレフィン共重合体、または変性オレフィン共重合体と称することもある）の基本骨格となる重合体としては、エチレン／プロピレン共重合体、エチレン／プロピレン／ジエン共重合体、エチレン／ブテン－１共重合体、エチレン／オクテン－１共重合体、エチレン／ヘキセン－１共重合体、エチレン／４－メチルペンテン－１共重合体、エチレン／環状オレフィン共重合体等を挙げることができるが、これらに限定されるものではない。変性エチレン－αオレフィン共重合体（Ｃ）の含有量は３～３０質量％である。変性エチレン－αオレフィン共重合体（Ｃ）の含有量は、３～２０質量％が好ましく、３～１０質量％がより好ましく、３～８質量％がさらに好ましい。 An ethylene-α-olefin copolymer (C) having a functional group capable of reacting with the terminal group and / or the amide group of the main chain of the polyamide resin used in the present invention (hereinafter, modified ethylene-α-olefin copolymer or modified olefin). Polymers that form the basic skeleton of (sometimes referred to as copolymers) include ethylene / propylene copolymers, ethylene / propylene / diene copolymers, ethylene / butene-1 copolymers, and ethylene / octene-1 polymers. Examples thereof include, but are not limited to, polymers, ethylene / hexene-1 copolymers, ethylene / 4-methylpentene-1 copolymers, and ethylene / cyclic olefin copolymers. The content of the modified ethylene-α-olefin copolymer (C) is 3 to 30% by mass. The content of the modified ethylene-α-olefin copolymer (C) is preferably 3 to 20% by mass, more preferably 3 to 10% by mass, still more preferably 3 to 8% by mass.

本発明で用いる変性エチレン－αオレフィン共重合体（Ｃ）におけるポリアミド樹脂の末端基および／または主鎖のアミド基と反応しうる官能基とは、ポリアミド樹脂の末端基であるアミノ基、カルボキシル基および主鎖のアミド基と反応しうる基であり、具体的にはカルボン酸基、酸無水物基、エポキシ基、オキサドリン基、アミノ基、イソシアネート基等が例示されるが、これらの中では酸無水物基が最も反応性に優れているので好ましい。また官能基の量は当然のことであるが、多い方がポリアミド樹脂との反応が進み、エチレン－αオレフィン共重合体はポリアミド樹脂の連続相の中でより微細な粒径で分散し、組成物の耐衝撃性も向上する。これらの官能基を有するエチレン－αオレフィン共重合体の製造法は共重合体を製造する工程で上記の官能基を持つ化合物を反応させる方法や共重合体のペレットと官能基を持つ化合物等を混合し、押出機等で混錬して反応させる方法等があるが、これらに限定されるものではない。 The functional group capable of reacting with the terminal group and / or the amide group of the main chain of the polyamide resin in the modified ethylene-α-olefin copolymer (C) used in the present invention is an amino group or a carboxyl group which is a terminal group of the polyamide resin. And a group that can react with the amide group of the main chain, and specific examples thereof include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxadrin group, an amino group, and an isocyanate group. Among these, an acid is exemplified. An anhydride group is preferable because it has the highest reactivity. The amount of the functional group is natural, but the larger the amount, the more the reaction with the polyamide resin proceeds, and the ethylene-α-olefin copolymer is dispersed in the continuous phase of the polyamide resin with a finer particle size and has a composition. The impact resistance of objects is also improved. The method for producing an ethylene-α-olefin copolymer having these functional groups includes a method of reacting the above-mentioned compound having a functional group in the step of producing the copolymer, a method of reacting the above-mentioned compound having a functional group, a pellet of the copolymer and a compound having a functional group, and the like. There are methods such as mixing and kneading with an extruder or the like to react, but the present invention is not limited to these.

本発明で用いる変性エチレン－αオレフィン共重合体（Ｃ）は、平均粒径２μｍ以下の粒子状で、連続相であるポリアミド樹脂中に分散するモルフォロジー構造を持つことが好ましい。上記のモルフォロジー構造は、組成物の製造工程でポリアミド樹脂と変性エチレン－αオレフィン共重合体が反応することにより得られる。ポリアミド樹脂中に変性エチレン－αオレフィン共重合体が２μｍ以下の平均粒径で微分散することにより、高い衝撃特性が得られる。 The modified ethylene-α-olefin copolymer (C) used in the present invention is preferably in the form of particles having an average particle size of 2 μm or less and having a morphological structure dispersed in a polyamide resin having a continuous phase. The above morphological structure is obtained by reacting a polyamide resin with a modified ethylene-α-olefin copolymer in the process of producing the composition. High impact characteristics can be obtained by finely dispersing the modified ethylene-α-olefin copolymer in the polyamide resin with an average particle size of 2 μm or less.

本発明で用いる導電性ポリエチレン樹脂（Ｄ）とは、導電性カーボンブラックが予めポリエチレン中に分散含有されているものである。導電性ポリエチレン樹脂（Ｄ）は、その体積固有抵抗率が、１Ω・ｃｍ以上、１×１０７Ω・ｃｍ以下のものが好ましく、導電性カーボンブラックを５～２０質量％含有していることが好ましい。The conductive polyethylene resin (D) used in the present invention is one in which conductive carbon black is dispersed and contained in polyethylene in advance. The conductive polyethylene resin (D) preferably has a volume resistivity of 1 Ω · cm or more and 1 × 10 7 Ω · cm or less, and preferably contains 5 to 20% by mass of conductive carbon black. preferable.

導電性ポリエチレン樹脂（Ｄ）を構成するポリエチレンは、エチレンの単独重合、又はエチレンと炭素数３～１２のα－オレフィン、例えば、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン等との共重合により得られる。また、改質を目的とする場合、ジエンとの共重合も可能である。このとき使用されるジエン化合物の例としては、ブタジエン、１，４－ヘキサジエン、エチリデンノルボルネン、ジシクロペンタジエン等を挙げることができる。
なお、重合の際のコモノマー含有率は、任意に選択することができるが、例えば、エチレンと炭素数３～１２のα－オレフィンとの共重合の場合には、エチレン・α－オレフィン共重合体中のα－オレフィン含有量は好ましくは０～４０モル％、より好ましくは０～３０モル％である。The polyethylene constituting the conductive polyethylene resin (D) may be homopolymerized with ethylene or an α-olefin having 3 to 12 carbon atoms of ethylene, for example, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl. It is obtained by copolymerization with -1-pentene, 1-octene and the like. Further, for the purpose of modification, copolymerization with a diene is also possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene and the like.
The comonomer content at the time of polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content thereof is preferably 0 to 40 mol%, more preferably 0 to 30 mol%.

導電性ポリエチレン樹脂（Ｄ）を構成するポリエチレンとしては、密度が０．９６以上の高密度ポリエチレンは、耐燃料性、摺動性の点で好ましい。
このような導電性ポリエチレン樹脂の市販品としては、Ｌｙｏｎｄｅｌｌｂａｓｅｌｌ社製の導電性ポリエチレンＧＭ９３５０Ｃ等が上げられる。As the polyethylene constituting the conductive polyethylene resin (D), high-density polyethylene having a density of 0.96 or more is preferable in terms of fuel resistance and slidability.
Examples of commercially available products of such conductive polyethylene resin include conductive polyethylene GM9350C manufactured by Lyondellbasell.

導電性ポリエチレン樹脂（Ｄ）を構成する導電性カーボンブラックは、アセチレンブラック、コンダクティブファーネスブラック、スーパーコンダクティブファーネスブラック、コンダクティブチャンネルブラック、１５００℃程度の高温で熱処理されたファーネスブラック又はチャンネルブラック等が例示され、ファーネスブラックの１種であるケッチェンブラックを挙げることが出来る。中でも一次粒子の中心が中空となっている中空シェル状構造のケッチェンブラックが好ましい。 Examples of the conductive carbon black constituting the conductive polyethylene resin (D) include acetylene black, conductive furnace black, super conductive furnace black, conductive channel black, furnace black heat-treated at a high temperature of about 1500 ° C., channel black and the like. , Ketjen Black, which is a kind of furnace black, can be mentioned. Of these, Ketjen Black, which has a hollow shell-like structure in which the center of the primary particles is hollow, is preferable.

導電性ポリエチレン樹脂（Ｄ）の含有量は１～２０質量％であり、２～１０質量％が好ましく、より好ましくは３～８質量％である。導電性ポリエチレン樹脂（Ｄ）が１質量％未満では耐燃料性の改善効果が小さく、２０質量％を超えると耐衝撃性が低下する虞がある。本発明の組成物では、ポリアミド樹脂中に分散している変性エチレン－αオレフィン共重合体と導電性ポリエチレン樹脂を構成するポリエチレンとは同類のオレフィン系樹脂で親和性が良いため、組成物中での分散性は良好で、導電性カーボンブラックが効率的に導電性を発現できる。 The content of the conductive polyethylene resin (D) is 1 to 20% by mass, preferably 2 to 10% by mass, and more preferably 3 to 8% by mass. If the conductive polyethylene resin (D) is less than 1% by mass, the effect of improving fuel resistance is small, and if it exceeds 20% by mass, the impact resistance may be lowered. In the composition of the present invention, the modified ethylene-α-olefin copolymer dispersed in the polyamide resin and the polyethylene constituting the conductive polyethylene resin are similar olefin resins and have good affinity with each other. The dispersibility is good, and the conductive carbon black can efficiently develop conductivity.

本発明の導電性ポリアミド樹脂組成物は、そのモルフォロジー構造が極めて重要である。ポリアミド樹脂（Ａ）がマトリックスとなる連続相を構成し、そのポリアミド樹脂と反応することにより、微分散している変性エチレン－αオレフィン共重合体（Ｃ）の分散平均粒径は２μｍ以下となり得る。さらに導電性カーボンブラック（Ｂ）は、粒子表面に存在する官能基と混練条件により連続相であるポリアミド樹脂（Ａ）中に、含有量の８０質量％以上が分散している。また導電性ポリエチレン樹脂（Ｄ）は、微分散している変性エチレン－αオレフィン共重合体（Ｃ）との親和性により、導電性カーボンブラックを含有したまま均一分散している。このため、ポリエチレン中の導電性カーボンブラックが、ポリアミド樹脂中の導電性カーボンブラック（Ｂ）に近接でき、組成物の導電性発現に寄与できる。さらに、燃料やアルコール含有燃料による膨潤が起こりにくいポリエチレンによって、導電性カーボンブラックの吸油性が発現しにくくなっているため、燃料やアルコール含有燃料による導電性の低下が抑制可能となる。 The morphological structure of the conductive polyamide resin composition of the present invention is extremely important. By forming a continuous phase in which the polyamide resin (A) forms a matrix and reacting with the polyamide resin, the dispersed average particle size of the finely dispersed modified ethylene-α-olefin copolymer (C) can be 2 μm or less. .. Further, the conductive carbon black (B) has a content of 80% by mass or more dispersed in the polyamide resin (A) which is a continuous phase depending on the kneading conditions and the functional groups existing on the particle surface. Further, the conductive polyethylene resin (D) is uniformly dispersed while containing the conductive carbon black due to the affinity with the finely dispersed modified ethylene-α-olefin copolymer (C). Therefore, the conductive carbon black in polyethylene can be brought close to the conductive carbon black (B) in the polyamide resin, and can contribute to the development of conductivity of the composition. Further, since polyethylene, which is less likely to swell due to the fuel or the alcohol-containing fuel, makes it difficult for the oil-absorbing property of the conductive carbon black to be exhibited, it is possible to suppress the decrease in the conductivity due to the fuel or the alcohol-containing fuel.

前記したモルフォロジー構造に制御するためには、各成分の配合方法が重要となる。ポリアミド樹脂（Ａ）に、予め導電性カーボンブラック（Ｂ）を分散させた後、ポリアミド樹脂と反応しうる反応性官能基を有するエチレン－αオレフィン共重合体（Ｃ）と、導電性ポリエチレン樹脂（Ｄ）を配合して、導電性ポリアミド樹脂組成物とすることが有効である。 In order to control the morphology structure described above, the method of blending each component is important. After dispersing the conductive carbon black (B) in the polyamide resin (A) in advance, the ethylene-α-olefin copolymer (C) having a reactive functional group capable of reacting with the polyamide resin and the conductive polyethylene resin ( It is effective to add D) to obtain a conductive polyamide resin composition.

本発明の導電性ポリアミド樹脂組成物には上述した（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）の成分の他に、通常のポリアミド樹脂組成物に用いられる耐候性改良材である銅酸化物、および／又はハロゲン化アルカリ金属、光または熱安定剤としてフェノール系酸化防止剤やリン系酸化防止剤、離型剤、結晶核剤、滑剤、顔料、染料等を含有しても良い。
本発明の導電性ポリアミド樹脂組成物は、（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）の各成分の合計で、８０質量％以上を占めることが好ましく、９０質量％以上を占めることがより好ましく、９５質量％以上を占めることがさらに好ましい。In addition to the components (A), (B), (C) and (D) described above, the conductive polyamide resin composition of the present invention contains copper, which is a weather resistance improving material used in ordinary polyamide resin compositions. Oxides and / or alkali metal halides, light or heat stabilizers may contain phenol-based antioxidants, phosphorus-based antioxidants, mold release agents, crystal nucleating agents, lubricants, pigments, dyes and the like.
The conductive polyamide resin composition of the present invention preferably occupies 80% by mass or more, and occupies 90% by mass or more, in total of each component of (A), (B), (C) and (D). Is more preferable, and it is further preferable to occupy 95% by mass or more.

本発明の導電性ポリアミド樹脂組成物は各成分を混合して、単に押出機で混錬するだけでは安定したモルフォロジー構造を形成することができず、特別の方法により混錬することが推奨される。例えば、溶融混錬機（例えば二軸押出機や溶融反応釜等々）にポリアミド樹脂（Ａ）と導電性カーボンブラック（Ｂ）とを溶融混錬し、ポリアミド樹脂中にカーボンブラックを均一に分散させた後、変性エチレン－αオレフィン共重合体（Ｃ）と導電性ポリエチレン樹脂（Ｄ）、および必要に応じて他の添加物を加えて更に溶融混錬する。このような二段階の溶融混錬をすることにより、本発明のモルフォロジー構造を持つポリアミド導電性樹脂組成物が安定して製造することができる。しかし、本発明のポリアミド導電性樹脂組成物の製造では、かかる特定のブレンド、溶融混錬方法に限られるものではなく、前記の組成およびモルフォロジー構造が得られる限り他のブレンド、溶融方法を用いて本発明の組成物を製造することができる。 In the conductive polyamide resin composition of the present invention, it is not possible to form a stable morphology structure simply by mixing each component and kneading with an extruder, and it is recommended to knead by a special method. .. For example, the polyamide resin (A) and the conductive carbon black (B) are melt-kneaded in a melt kneader (for example, a twin-screw extruder, a melt reaction kettle, etc.) to uniformly disperse the carbon black in the polyamide resin. After that, the modified ethylene-α-olefin copolymer (C), the conductive polyethylene resin (D), and if necessary, other additives are added and further melt-kneaded. By performing such two-step melt kneading, the polyamide conductive resin composition having the morphological structure of the present invention can be stably produced. However, the production of the polyamide conductive resin composition of the present invention is not limited to such a specific blending and melt kneading method, and other blending and melting methods can be used as long as the above composition and morphological structure can be obtained. The composition of the present invention can be produced.

以下に実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例に何ら制限されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

また以下の実施例、比較例において示した各特性、物性値は下記の試験方法で測定した。試験片は射出成形機（東芝機械（株）製、ＩＳ８０）により下記条件にて成形した。
樹脂温度：２７５℃
金型温度：４０℃
射出圧力：５０ｋｇ／ｃｍ２
射出時間：１秒
保圧力：６０ｋｇ／ｃｍ２
保持時間：６秒In addition, each characteristic and physical property value shown in the following Examples and Comparative Examples were measured by the following test method. The test piece was molded by an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS80) under the following conditions.
Resin temperature: 275 ° C
Mold temperature: 40 ° C
Injection pressure: 50 kg / cm 2
Injection time: 1 second Holding pressure: 60 kg / cm 2
Retention time: 6 seconds

１．体積固有抵抗
射出成形で得た１００ｍｍ×１００ｍｍ×２ｍｍ（厚み）のプレートのゲート位置に対し直角方向の両端に端子を接続し、デジタルマルチメーター（アドバンテスト（株）製、ＴＲ－６８４３）で測定した。なお測定試験片は７０℃で１２時間、真空乾燥した後、２０℃、５０％ＲＨの雰囲気で２４時間シーズニングしてから測定した。1. 1. Volume resistivity The terminals were connected to both ends in the direction perpendicular to the gate position of the 100 mm × 100 mm × 2 mm (thickness) plate obtained by injection molding, and measured with a digital multimeter (TR-6843, manufactured by Advantest Co., Ltd.). .. The measurement test piece was vacuum-dried at 70 ° C. for 12 hours, and then seasoned at 20 ° C. in an atmosphere of 50% RH for 24 hours before measurement.

２．体積固有抵抗（燃料暴露後）
テストピース浸漬用のＣＭ１５燃料は、Ｆｕｅｌ－Ｃ（イソオクタン／トルエン＝１／１（容量））にメタノール（ナカライテスク社製 純度９９．５％）を１５質量％になるよう混合して作製した。そこに、１．で使用したテストピースを浸漬し、６０℃オーブン中に静置して試験を実施した。
テストピースは１６８時間浸漬後にＣＭ１５燃料から取り出した後、表面に付着した溶液をふき取った後、１分以内に１．と同様の方法で体積固有抵抗を測定した。2. 2. Volume resistivity (after fuel exposure)
The CM15 fuel for dipping the test piece was prepared by mixing Fuel-C (isooctane / toluene = 1/1 (volume)) with methanol (purity 99.5% manufactured by Nacalai Tesque) so as to be 15% by mass. There, 1. The test piece used in 1 was immersed and allowed to stand in an oven at 60 ° C. to carry out the test.
The test piece was soaked for 168 hours, removed from the CM15 fuel, wiped off the solution adhering to the surface, and then within 1 minute. The volume resistivity was measured by the same method as in.

３．ノッチ入りシャルピー衝撃強度
低温シャルピー衝撃強度：ＩＳＯ－１７９－１ｅＡに準じて、射出成形でダンベル片を作製して－４０℃で測定した。3. 3. Charpy impact strength with notch Low temperature Charpy impact strength: A dumbbell piece was prepared by injection molding according to ISO-179-1eA and measured at -40 ° C.

４．メルトインデックス
ＩＳＯ１１３３に準拠して測定した。温度２５０℃、荷重１０ｋｇｆで測定した。4. Measured according to Melt Index ISO1133. The measurement was carried out at a temperature of 250 ° C. and a load of 10 kgf.

５．モルフォロジー構造の観察
射出成形で得た１００ｍｍ×１００ｍｍ×２ｍｍ（厚み）のプレートの中央部より凍結切片を作製した。
変性エチレン－αオレフィン共重合体（Ｃ）の平均粒子径の測定には、試料の樹脂流れの方向と垂直な断面の凍結切片を作製し、５％リンタングステン酸水溶液で３０分間染色し、さらにカーボン蒸着を施した後、日本電子製ＪＥＭ２０１０透過型電子顕微鏡で加速電圧２００ＫＶ、直接倍率５０００倍で観察して、写真撮影をした。次いで、得られた写真を画像解析装置に供することによって、平均粒子径を求めた。当該装置では、ドメイン（分散相）の観察像が楕円形状である場合は、球に換算した直径を粒子径とした。換算は、楕円の長径と短径の平均を球の直径とした。
導電性カーボンブラック（Ｂ）の存在場所は、得られた写真に存在する全てのカーボンブラックの粒子数と連続相に存在するカーボンブラックの粒子数を画像解析装置でカウントして、連続相に存在する導電性カーボンブラック（Ｂ）の粒子数の百分率％を質量％とした。なお、導電性ポリエチレン樹脂（Ｄ）中のカーボンブラックは、分散相の内、変性エチレン－αオレフィン共重合体（Ｃ）以外の分散相中に存在しており、導電性カーボンブラック（Ｂ）とは区別可能であり、写真中に存在するカーボンブラックにはカウントしなかった。5. Observation of morphology structure A frozen section was prepared from the center of a 100 mm × 100 mm × 2 mm (thickness) plate obtained by injection molding.
To measure the average particle size of the modified ethylene-α-olefin copolymer (C), prepare frozen sections with a cross section perpendicular to the direction of the resin flow of the sample, stain with a 5% phosphotung acid aqueous solution for 30 minutes, and further. After carbon vapor deposition, observation was performed with a JEM2010 transmission electron microscope manufactured by JEOL Ltd. at an acceleration voltage of 200 KV and a direct magnification of 5000 times, and a photograph was taken. Then, the obtained photograph was subjected to an image analysis device to obtain an average particle size. In this device, when the observation image of the domain (dispersed phase) has an elliptical shape, the diameter converted into a sphere is used as the particle diameter. For conversion, the average of the major axis and the minor axis of the ellipse was taken as the diameter of the sphere.
The location of the conductive carbon black (B) is present in the continuous phase by counting the number of all carbon black particles present in the obtained photograph and the number of carbon black particles present in the continuous phase with an image analyzer. The percentage% of the number of particles of the conductive carbon black (B) to be used was defined as% by mass. The carbon black in the conductive polyethylene resin (D) is present in the dispersed phase other than the modified ethylene-α-olefin copolymer (C) among the dispersed phases, and is different from the conductive carbon black (B). Was distinguishable and did not count towards the carbon black present in the photo.

実施例および比較例に用いた組成物の原材料は、下記のような材料を使用した。
ポリアミド樹脂（Ａ）
Ａ－１：東洋紡ナイロンＴ－８４０（東洋紡（株）製、ポリアミド６、相対粘度２．２）
導電性カーボンブラック（Ｂ）
Ｂ－１：ファーネスカーボン １００（ライオン（株）製）
Ｂ－２：ケッチェンカーボンＥＣ（ライオン（株）製）
変性エチレン－αオレフィン共重合体（Ｃ）
Ｃ－１：変性オレフィン共重合体 タフマー（登録商標）ＭＨ７０２０（三井化学（株）製 無水マレイン酸変性エチレン－αオレフィン共重合体）
導電性ポリエチレン樹脂（Ｄ）
Ｄ－１：導電性ポリエチレンＧＭ９３５０Ｃ（Ｌｙｏｎｄｅｌｌｂａｓｅｌｌ社製 高密度ポリエチレンに導電性カーボンブラック１０質量％が分散）
Ｄ－２：導電性ポリエチレン カーボン２０質量％開発品（Ｌｙｏｎｄｅｌｌｂａｓｅｌｌ社製 高密度ポリエチレンに導電性カーボンブラック２０質量％が分散）
Ｄ’：高密度ポリエチレンＭＭＥ００１（三井化学（株）製）The following materials were used as raw materials for the compositions used in Examples and Comparative Examples.
Polyamide resin (A)
A-1: Toyobo Nylon T-840 (manufactured by Toyobo Co., Ltd., polyamide 6, relative viscosity 2.2)
Conductive carbon black (B)
B-1: Furness Carbon 100 (manufactured by Lion Corporation)
B-2: Ketjen Carbon EC (manufactured by Lion Corporation)
Modified ethylene-α-olefin copolymer (C)
C-1: Modified olefin copolymer Toughmer (registered trademark) MH7020 (maleic anhydride-modified ethylene-α-olefin copolymer manufactured by Mitsui Chemicals, Inc.)
Conductive polyethylene resin (D)
D-1: Conductive polyethylene GM9350C (10% by mass of conductive carbon black dispersed in high-density polyethylene manufactured by Lyondellbasell)
D-2: Conductive polyethylene carbon 20% by mass Developed product (20% by mass of conductive carbon black is dispersed in high-density polyethylene manufactured by Lyondellbasell)
D': High-density polyethylene MME001 (manufactured by Mitsui Chemicals, Inc.)

（実施例および比較例）
全体のコンパウンディングの前に、まず、ポリアミド樹脂と導電性カーボンブラックとを、表１に記載の質量比率になるように二軸押出機（池貝鉄工（株）製、ＰＣＭ３０）で溶融混練してマスターバッチペレットとした。次いで、得られたマスターバッチペレットを用い、表１の組成割合で各原料を計量ブレンドし、シリンダー温度２６０℃に設定した二軸押出機（池貝鉄工（株）製、ＰＣＭ３０）で溶融混練して導電性ポリアミド樹脂組成物ペレットを得た。得られた導電性ポリアミド樹脂組成物を用いて、各評価を行った。結果を表１に記す。(Examples and comparative examples)
Before the whole compounding, first, the polyamide resin and the conductive carbon black are melt-kneaded with a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM30) so as to have the mass ratio shown in Table 1. It was made into a master batch pellet. Next, using the obtained masterbatch pellets, each raw material was weighed and blended at the composition ratio shown in Table 1, and melt-kneaded with a twin-screw extruder (manufactured by Ikegai Iron Works Co., Ltd., PCM30) set to a cylinder temperature of 260 ° C. Conductive polyamide resin composition pellets were obtained. Each evaluation was performed using the obtained conductive polyamide resin composition. The results are shown in Table 1.

Figure 0007056557000001
Figure 0007056557000001

比較例１、２、３の導電性ポリアミド樹脂組成物は、ＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗が１×１０７Ω・ｃｍを超えることが確認できた。It was confirmed that the conductive polyamide resin compositions of Comparative Examples 1, 2 and 3 had a volume resistivity exceeding 1 × 107 Ω · cm after being exposed to the CM15 fuel for 168 hours.

本発明によれば、バイオエタノールを使用する自動車の部材、電気・電子製品の部品用として利用が可能である。
According to the present invention, it can be used for automobile parts and electric / electronic product parts using bioethanol.

Claims (3)

ポリアミド樹脂（Ａ）８４～４０質量％、導電性カーボンブラック（Ｂ）５～３０質量％、ポリアミド樹脂の末端基および／又は主鎖のアミド基と反応しうる反応性官能基を有するエチレン－αオレフィン共重合体（Ｃ）３～３０質量％、および導電性ポリエチレン樹脂（Ｄ）１～２０質量％を含有してなり、
導電性カーボンブラック（Ｂ）は、連続相であるポリアミド樹脂（Ａ）中に、含有量の８０％以上が分散しており、
導電性ポリエチレン樹脂（Ｄ）中のカーボンブラックは、分散相の内、変性エチレン－αオレフィン共重合体（Ｃ）以外の分散相中に存在している、
下記の特性（イ）、（ロ）を満足することを特徴とする導電性ポリアミド樹脂組成物。
（イ）導電性ポリアミド樹脂組成物を射出成形することによって得た平板（１００ｍｍ×１００ｍｍ×２ｍｍ（厚み））の初期の体積固有抵抗が１×１０ ５ Ω・ｃｍ以下で、該平板をＣＭ１５燃料に１６８時間暴露した後の体積固有抵抗が１×１０ ７ Ω・ｃｍ以下
（ロ）導電性ポリアミド樹脂組成物を射出成形することによって得た試験片の－４０℃におけるシャルピー衝撃強度が２．０ＫＪ／ｍ２以上 Polyamide resin (A) 84-40% by mass, conductive carbon black (B) 5-30% by mass, ethylene-α having a reactive functional group capable of reacting with the terminal group and / or the amide group of the main chain of the polyamide resin. It contains 3 to 30% by mass of the olefin copolymer (C) and 1 to 20% by mass of the conductive polyethylene resin (D).
80% or more of the content of the conductive carbon black (B) is dispersed in the polyamide resin (A) which is a continuous phase.
The carbon black in the conductive polyethylene resin (D) is present in the dispersed phase other than the modified ethylene-α-olefin copolymer (C) among the dispersed phases.
A conductive polyamide resin composition characterized by satisfying the following characteristics (a) and (b).
(A) The initial volume resistivity of the flat plate (100 mm × 100 mm × 2 mm (thickness)) obtained by injection molding the conductive polyamide resin composition is 1 × 10 5 Ω · cm or less, and the flat plate is used as CM15 fuel. Volume resistivity after exposure to 168 hours is 1 × 10 7 Ω · cm or less (b) The shearpy impact strength of the test piece obtained by injection molding the conductive polyamide resin composition at -40 ° C is 2.0 KJ. / M 2 or more 前記導電性ポリアミド樹脂組成物が、下記の特性（ハ）を満足する請求項１に記載の導
電性ポリアミド樹脂組成物。
（ハ）温度２５０℃、荷重１０ｋｇｆで測定したメルトインデックスが、２ｇ／１０ｍ
ｉｎ以上 The conductive polyamide resin composition according to claim 1, wherein the conductive polyamide resin composition satisfies the following property (c).
(C) The melt index measured at a temperature of 250 ° C. and a load of 10 kgf is 2 g / 10 m.
in or more 前記導電性ポリエチレン樹脂（Ｄ）のポリエチレンが、高密度ポリエチレンである請求
項１または２に記載の導電性ポリアミド樹脂組成物。 The conductive polyamide resin composition according to claim 1 or 2, wherein the polyethylene of the conductive polyethylene resin (D) is a high-density polyethylene.
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